Petroleum reactions with chlorine dioxide

The direct reaction of paraffinic petroleum fractions to alkyl sulfonates by the Reed process has been extensively investigated in this country. In this process paraffin-rich stocks are reacted with sulfur dioxide and chlorine (16) and processed to sulfonates as indicated by the equations ... 

Diorgano tellurium compounds can be easily converted to diorgano tellurium dihalides in reactions with sulfuryl chloride, bromide, and iodide. Carbon tetrachloride, dichlorometh-ane, diethyl ether, petroleum ether, or benzene have been used as reaction media. Chlorinations with sulfuryl chloride, a liquid reagent, avoid the use of gaseous chlorine. Required amounts of sulfuryl chloride can be more easily measured than those of chlorine. Sulfur dioxide formed during the reaction escapes the reaction mixture as a gas, thus facilitating the isolation of the product. For these reasons, sulfuryl chloride has been frequently used, whereas sulfuryl bromide and iodide5-6 have been only infrequently employed. 

Detergents, which now rival soap in demand, are based largely on petroleum the variety of structures which confer detergent properties have led to some interesting syntheses. Alkyl aryl sulfonates are made by alkylation of benzene either with chlorinated kerosene or with a highly-branched olefin made from propylene. Long chain olefins for secondary sulfates were made from paraffin wax. Secondary alkyl sulfonates were made by direct sulfonation of paraffins with sulfur dioxide and chlorine, a reaction discovered in America in the 193O s. 

NITROGEN DIOXIDE (10102-44-0) A powerful oxidizer. Reacts with water, forming nitric acid and oxygen. Violent reaction with strong reducing agents, anhydrous ammonia, alcohols, chlorinated hydrocarbons, cyclohexane, ethers, fluorine, formaldehyde, fuels, nitrobenzene, oxygen difluoride, petroleum, sodium, toluene. Incompatible with combustible materials, red phosphorus, petroleum products. Forms explosive material with propylene. Vapor reacts violently with phospham. Attacks many metals in the presence of moisture. 

Instead of the use of sulfuryl chloride, SO2 and CI2, which combine to give sulfuryl chloride, can be employed for vapor-phase reactions. When the ratio of SO2 to CI2 is adjusted, it is feasible to produce sulfonic or chlorosulfonic acid derivatives of saturated paraffins in liquid-phase reactions. According to Lockwood and Richmond, a premixed stream of sulfur dioxide and chlorine can be used for the countercurrent photochlorination of white oil (petroleum fraction, sp gr, 0.8033 bp, 283-324 C) at about 50°C. The product, after hydrolysis with 30 per cent sodium hydroxide, yields an aqueous solution of the sodium salt of a sulfonic or chlorosulfonic acid. An increase in the ratio of SO2 to CI2 greatly increases the yield of solubilized product. When a 3 1 ratio is used, the product contains very little chlorine and has good wetting and detergent characteristics. ... 

The principal ore of titanium is ilmenite or ferrous titanate (FeTiOa), and this is the ore mainly used for the production of ferrotitanium by a smelting process. However, its use directly for the production of titanium tetrachloride would be extremely wasteful of chlorine, since a high proportion of this reagent would be used for the production of unwanted ferric chloride. Consequently, chlorination generally involves the less plentiful ore of titanium, rutile, the dioxide (TiOa), which is found in the form of black river and beach sands. This is mixed with ground charcoal or petroleum coke, briquetted, and volatile material removed by heating to 500 to 800°C. Chlorination can be carried out at 700 to 1000°C in a conventional vertical furnace, and the reaction is sufficiently exothermic for it to proceed without the application of external heat, except to raise the temperature of the reactants initially. The reaction may be represented approximately as ... 

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